Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process

ABSTRACT

The invention relates to a process for the preparation of an ammonia synthesis catalyst based on fused and reduced iron oxide, with or without traces of a promoter oxide of aluminum, calcium, potassium, magnesium or silicon, in which the fused and reduced iron oxide is aftertreated with an aqueous solution of a cerium salt or with an aqueous solution of a mischmetal salt, including a cerium salt.

The present invention relates to a process for the preparation of an ammonia synthesis catalyst and, in particular, to the preparation of an ammonia synthesis catalyst based on reduced iron oxide.

It is well known to prepare catalysts for the synthesis of ammonia by fusing iron oxide, followed by reduction. Many methods for the proparation of ammonia synthesis catalysts have been proposed but none have been satisfactory from the point of view of the yield of ammonia obtained, especially at lower synthesis temperatures.

In order to improve the performance of the catalyst, it has been proposed to add to iron oxide before fusion traces of oxides of other metals, such as the oxides of aluminum, calcium, potassium, magnesium, and silicon. It has also been proposed to add to iron oxide before fusion a small quantity of cerium oxide or of a cerium salt.

None of these methods for the preparation of ammonia synthesis catalysts have made it feasible to produce ammonia at temperatures of less than about 900° to 1020° F which require special expensive equipment.

It has now been discovered that ammonia synthesis catalysts which make ammonia production possible at lower temperatures and/or lower pressures can be prepared if the fused and reduced catalysts are aftertreated with an aqueous solution of a cerium salt.

It has further been discovered that all the air should preferably be evacuated from the pores of the catalysts before they are aftertreated with the aqueous solution of a cerium salt to ensure that the pores are thoroughly impregnated with the aqueous solution.

It is accordingly an object of this invention to prepare an ammonia synthesis catalyst which is particularly suitable for operating the ammonia synthesis at lower temperatures and/or pressure than has hitherto been possible.

It is a further object of this invention to prepare an ammonia synthesis catalyst of high efficiency at all operating temperatures and pressures for synthesizing ammonia from hydrogen and nitrogen.

Other objects of the invention will be clear from the discription which follows.

These objects are accomplished by fusing and reducing iron oxide, with or without other metallic oxides, and aftertreating the reduced oxide with an aqueous solution of a cerium salt or of a mischmetal salt.

Preferably, air is evacuated from the pores of the fused and reduced oxide, and the pores are impregnated with the aqueous solution of a cerium salt or of a mischmetal salt.

The preferred range of cerium to be added to the reduced catalyst is desirably from 0.1 to 1.5% by weight, preferably from 0.4 to 1% by weight. Effective results are obtained if cerium is added in an amount between 0.3 and 0.8 % by weight. Particularly effective results are obtained if the amount of cerium incorporated in the catalyst is between 0.45 and 0.7% by weight.

All water soluble salts of cerium will be suitable for incorporation in the reduced catalyst in accordance with the invention. The preferred cerium salt is cerous nitrate as it is most commonly available and adequately soluble. However, other water soluble salts of cerium, such as the acetate or the double salt, cerium ammonium nitrate, may also be used. Cerium salts may also be used in admixture with salts of other rare earth metals, for example those present in mischmetal. Instead of a salt of cerium alone, a mixture of the salts of cerium and other rare earth metals, such as the mischmetal nitrates, may therefore be used. Examples of other rare earth metals in mischmetal are lanthanum, didymium, yttrium, neodymium, praseodymium or ytterbium.

The invention is applicable to the improvement in the performance of ammonia synthesis iron catalysts to which traces of oxides of aluminum, calcium, potassium, magnesium, silicon and other elements have been added.

Tests conducted with the ammonia synthesis catalyst prepared in accordance with the process of this invention have shown a very high activity as evidenced by the considerable increase in the yield of ammonia obtained, when compared with the yield of ammonia under the same operating conditions obtained using catalysts prepared by other methods of incorporating cerium. As illustrated in Tables 3 to 5, the yield of ammonia is increased up to nearly 40% at comparable temperatures and pressures. Moreover, it is possible to operate at much lower temperatures and pressure to obtain excellent ammonia yields. Thus, the operating temperatures for the ammonia synthesis may be low as 750° to 900° F, suitably 800° to 880° F, and operating pressures used may be below 150 atmospheres. These are much lower than the operating temperatures using catalysts prepared by known methods, which are generally from 900° to 1020° F at a pressure of generally between 150 and 600 atmospheres.

Because of the lower temperature and lower pressure which can be used in the ammonia synthesis, synthesis converters may be used which do not require a double shell construction, with its attendant cost. The reduced capital cost may permit the construction of units of larger capacity at a cost comparable with the cost of smaller units of present construction. The lower temperature and pressure also affords operational savings as it reduces the energy requirements as well as the compressor investment.

The invention will now be illustrated by means of the following examples; but the scope of the invention is not to be limited thereby. Example 4 illustrates the testing of the catalysts.

EXAMPLE 1

a. Iron oxide, was mixed with traces of conventional promoters such as alumina, calcium oxide, potassium and silica. The raw materials used for the catalyst preparation were the following:

                  Table 1                                                          ______________________________________                                         Purified Natural Magnetite                                                                        100     parts by weight                                     (-20+60 mesh)                                                                  Alumina            3.5     "                                                   Potassium Nitrate  2.0     "                                                   Calcium Oxide      2.5     "                                                   Cerous Nitrate     10.0    "                                                   ______________________________________                                    

                  Table 2                                                          ______________________________________                                         Screen Fraction   % of Dry Ore                                                 (Tyler Standard)  in Fraction                                                  ______________________________________                                         +20 mesh          35.57                                                        -20 +60 mesh      43.75                                                        -60 mesh          20.68                                                        ______________________________________                                    

Natural magnetite ore was first dried in pans and then screened to yield three fractions. The intermediate fraction (-20 +60 mesh) was processed trough a magnetic separator to remove silica. The silica content was reduced from 2.39% to about 1%, which is close to the silica concentration in commercial catalysts. The amounts of undesirable impurities as finally determined in the fused catalyst showed 0.035% phosphorus and 0.0007% sulfur.

A small electric resistance fusion furnace was designed and installed for making ammonia synthesis catalyst. The furnace comprised a steel fusion trough, a brick and concrete supporting pier, fume removal hood, and two water-cooled iron electrodes. The fume hood served to remove the fumes of nitrogen oxides evolved during fusion and was connected to a caustic scrubber and to an exhaust fan. Two water-cooled iron electrodes supplied power to the furnace charge from a multi-step transformer. The primary voltage across the transformer at any step was regulated by a variac and this provided fine control up to 240V

The fusion trough was lined with high purity natural magnetite which served as refractory and insulation. It was important for controlling the purity of the product by using a refractory lining similar in composition to the material to be fused and containing a minimum of contaminants. The purified ore was arranged in the shell to form a shallow trough. The fusion pig was formed in the center between the two electrodes.

The iron electrodes supplied power to the furnace charge and were connected by a taut handmade chain prepared from an Armco iron wire which is covered with high purity natural magnetite fines and promoters. The function of the wire chain was to conduct the current initially and generate sufficient heat to produce a continuous molten core of iron oxides between the electrodes before melting itself. The molten core was conductive enough to carry the load thereafter. Armco iron rods, in 1/2 × 1 inch size were added to adjust the ferrous to ferric ratio of the catalyst to 0.5 as nearly as practical. The added iron compensated for atmospheric oxidation during fusion.

A typical fusion charge (exclusive of shell lining) contained about 50 pounds of material comprising:

    ______________________________________                                         Purified natural magnetite (-20 +60 mesh)                                                                  50 lbs.                                            Alumina                     1.75                                               Potassium nitrate           1.0                                                Calcium oxide               1.25                                               Armco iron (1/2"X1" rods and 13 gage wire chain)                                                           0.9-0.95                                           Cerous nitrate              5.0                                                ______________________________________                                    

The wire was tied to each electrode by wrapping it around two turns and was then tightened and twisted to hold. The connecting wire chain was manually formed and was located about 3 to 4 inches below the fusion trough surface. The distance between the electrodes was about 18 inches. The charging material after blending for two hours in a blender was distributed evenly along the wire chain to form a mound. The iron rods were placed within the mound.

About 30 V. (the secondary voltage) was applied to the wire chain and was later decreased to about 15 V. gradually over a period of about an hour. As the fusion continued, the resistance between the electrodes decreased, and the primary voltage was dropped by adjusting the variac setting to keep the total KW less than 12.0. This was a limitation of the electrical equipment available. Current varied during the fusion period but was later held constant at about 640 Amp. The power varied during the run from a maximum of about 10 KW in the early part to 6.0 to 6.5 KW toward the end. Total time required to make a fusion was about 5.0 hours.

On completing a fusion, the circuit was then opened. The pig was allowed to cool overnight before being removed. The unfused and semi-fused material was removed with a wire brush from the surface of the pig. The pig was broken up with a sledge hammer first and then fed to a jaw crusher. The material was then crushed and screened. The -7 +14 mesh (1 to 3 mm size) fraction was recovered as the product. Total material charged to fusion trough was about 48.5 lbs. A pig of 19 lbs. was recovered. After crushing and screening it was classified as follows:

    ______________________________________                                         +7 mesh        3.09    lbs.   16.3%                                            -7 +14 mesh    6.46           34.0%                                            -14 mesh       9.33           49.1%                                            loss           0.12           0.6%                                             ______________________________________                                    

The oversize material (+7 mesh) was recycled for further size reduction and product recovery. The undersize material was recycled to another fusion. The power consumption for a typical fusion was about 34.5 KW-HR.

The fused catalyst prepared was reduced by hydrogen alone. However, reduction may also be effected with a hydrogen-nitrogen gas. The removal of oxygen by reduction changed the catalyst structure by generating porosity and inner surface areas.

The reduced iron catalyst was pyrophoric in contact with air even at ambient temperature and also very sensitive to poisons. Thus prereduced catalysts were stabilized after reduction. Stabilization consisted of a surface oxidation of the catalyst whereby it takes up an amount of oxygen in the order of 2.0 wt%. The oxygen is removed in the subsequent reduction. This restores the activity of the catalyst.

A 2 inches heavy wall reactor 58 inches long, was installed for catalyst reduction and stabilization. Six thermocouples were installed along the reactor length to indicate the skin temperatures. The procedure for a typical run was as follows:

1. A larger particle size catalyst (6-10 mm) was loaded in between thermocouples--3 to thermocouple--1 to serve as a gas preheater.

2. 1814 gms (-7 +14 mesh) unreduced catalyst was then charged. This bed extended from thermocouple--6 to thermocouple--3 with a screen support at the bottom of this bed.

3. The reactor was pressured to 950-1000 psig using hydrogen gas.

4. Once-through hydrogen flow at a rate of 14.5 SCFH was used.

5. Reactor temperature was raised to 650° F at a rate of 100° F/hr.

6. After reaching 650° F, the rate of heating was decreased to about 25° F/hr. Hydrogen flow increased to 56.0 SCFH (Sp. Vel. = 2100 hr.sup.⁻¹). Start of catalyst reduction was indicated by the appearance of water in a sample collection bottle.

7. The reactor temperature was brought up to 960° F in about 10 hours.

8. Reactor temperature was maintained at 960° F for about 60 hours. The catalyst was well reduced at this point and the exit gas essentially dry. Hydrogen flow was cut off.

9. The peak temperature in reactor was maintained below 975° F.

10. Pressure was reduced to 75 psig. The reactor was cooled to below 150° F by high nitrogen flow in about 4 hours.

11. A mixture of 1% oxygen and 99% nitrogen was passed through the reactor and left in for about 10 hours. Maximum temperature in the reactor was maintained at below 200° F.

12. As the thermocouple readings approached 200° F, oxygen was cut off in the gas mixture and the reactor purged with nitrogen for about 15 minutes.

13. A mixture of 5% oxygen --95% nitrogen gas was passed into reactor and left in for about 3 hours. Maximum temperature in the reactor was maintained at below 200° F.

14. The catalyst was cooled to less than 120° F by purging with nitrogen.

15. The catalyst was removed from reactor and kept in a sealed bottle.

16. 1434 gm of prereduced catalyst were recovered from the unit.

17. An analysis of the catalyst indicated 2.85% by weight of cerium.

EXAMPLE 2

a. The reduced catalyst was prepared as in Example 1 above, except that no cerium nitrate was added before the fusion.

b. 8.0 gm of cerous nitrate Ce(NO₃)₃.6H₂ O was dissolved in 200 gm of deionized water at room temperature. 350 gm of the reduced catalyst to be impregnated was first put into a closed vessel and evacuated. After the vacuum reached a level of 5-10 mm Hg., the cerium solution contained in a separator funnel on top of the closed vessel was added. About 175-180 cc of cerium solution was allowed to flow into the closed vessel, with the remaining 20-25 cc of solution left in the funnel to provide a seal to prevent air leakage into the vessel. There should be sufficient solution to immerse all the catalyst particles. After addition of the solution, the vessel was shaken for about 2-4 minutes to make sure that all the catalyst had been thoroughly contacted by the cerium solution. Finally the stopcock was opened and the rest of solution allowed to enter the closed vessel. After one minute the excess amount of solution (about 145 to 150 cc) was drained off and the wet catalyst dried in a laboratory oven under vacuum for about 2.0 hours at 300° F. A catalyst treated in this manner generally contains an amount of cerium ranging from 0.1 to 1.2 wt%.

EXAMPLE 3

a. The reduced catalyst was prepared as in Example 1 above, except that no cerium nitrate was added before the fusion.

b. 2.5 gm of cerous nitrate was dissolved in 100 gm water and soaked into 200 gm of the reduced iron catalyst. The excess amount of the solution was drained off. Final analysis indicated a cerium content of 0.4 wt% of total catalyst.

EXAMPLE 4

The activity of the ammonia catalysts was tested as follows:

250 gm of catalyst (1 to 3 mm size) was charged each time to a test converter. Five thermocouples extended into the catalyst bed to indicate temperatures. The gas used was a 3H₂ :1N₂ mixture. A deoxo unit and a gas purifier were installed in the make-up gas line for oxygen, water and foreign particles removal. The make-up gas flow rate was measured by a flow-meter. It was compressed to the desired pressure by a gas compressor. The make-up then combined with recycled gas, which was measured by a flow-meter. The combined gas was passed through gas preheater and was preheated to 400° - 750° F depending on operating conditions. The combined gas was then introduced into the reactor, first through the wrapped copper coils around the catalyst bed and then down through the catalyst bed. The effluent gas from the reactor was passed to a water cooled condenser and a Freon cooled condenser in series. Ammonia made was accumulated in a product receiver. The recycle gas consisted of nitrogen, hydrogen and saturated ammonia vapor and was compressed through a gas recirculation compressor. A part of the recirculated gas was purged before compression to avoid the buildup of any inerts in the system. The purge gas rate was measured by a flow-meter. Ammonia conversion was determined by scrubbing reactor exit gas samples of known volume with excess sulfuric acid and back titrating with standard sodium hydroxide, using methyl red as indicator. The ammonia content thus determined was compared with the equilibrium ammonia content at any given temperature and pressure.

The results obtained using cerium nitrate added before fusion and cerium nitrate or a mischmetal additive as an aftertreating agent are shown in the accompanying Tables 3 to 5.

As will be noted, the efficiency of the catalyst when aftertreated with an aqueous solution of a cerium salt is substantially increased at all temperature levels, as compared with catalyst to which cerium was added before fusion. Moreover, temperatures lower than those conventionally used may be employed in the ammonia synthesis when using a catalyst aftertreated with an aqueous solution of a cerium salt as the efficiency reading at these lower temperatures is sufficiently high.

Having now fully disclosed with particularity preferred modes by which my invention may be carried out, various modifications and alterations within the spirit and scope of my invention, as claimed, will occur to those in the art.

                                      TABLES 3 - 5                                 __________________________________________________________________________     Reactor                                                                             Receiver                                                                             Preheater                                                                            CATALYST BED TEMPERATURES, ° F                                                            Space                                                                              Re-  Make-                                                                               Reactor                                                                             Equili-                                                                             Effi-               Pressure                                                                            Temp. Temp.                   Vel.                                                                               cycle                                                                               up Gas                                                                              Outlet                                                                              brium                                                                               ciency              PSIG t.sub.2, ° F                                                                  t.sub.3, ° F                                                                  t.sub.4                                                                           t.sub.5                                                                           t.sub.6                                                                           t.sub.7                                                                           t.sub.8                                                                           t.sub.avg.                                                                        Hr.sup.-.sup.1                                                                     NH.sub.3 %                                                                          H.sub.2 /N.sub.2                                                                    NH.sub.3 %                                                                          NH.sub.3 %                                                                          %                   __________________________________________________________________________     Table 3:                                                                       __________________________________________________________________________     Catalyst + Mischmetal (1-3 mm) Ce = 0.32% Fe.sup.+.sup.2 /Fe.sup.+.sup.3       = 0.65 Cerium added in Aftertreatment                                          2250 0     660   830                                                                               880                                                                               900                                                                               955                                                                               970                                                                               907                                                                               17,100                                                                             --   2.85 14.5 17.0 85.3                2250 0     655   830                                                                               875                                                                               895                                                                               945                                                                               960                                                                               901                                                                               16,700                                                                             1.78 2.98 15.0 17.4 86.2                2250 0     640   730                                                                               800                                                                               845                                                                               910                                                                               910                                                                               839                                                                               16,400                                                                             1.91 2.91 14.5 22.65                                                                               64.0                2250 0     640   730                                                                               800                                                                               840                                                                               910                                                                               900                                                                               836                                                                               16,400                                                                             --   2.91 15.9 22.95                                                                               69.3                2250 0     640   725                                                                               795                                                                               840                                                                               900                                                                               900                                                                               832                                                                               16,000                                                                             --   2.91 14.7 23.35                                                                               62.9                2250 0     595   670                                                                               740                                                                               785                                                                               840                                                                               800                                                                               767                                                                               15,300                                                                             --   2.91 11.8 31.2 37.8                2250 0     595   670                                                                               740                                                                               785                                                                               840                                                                               800                                                                               767                                                                               15,300                                                                             --   2.91 11.75                                                                               31.2 37.7                Table 4:                                                                       __________________________________________________________________________     Catalyst (1-3 mm) Ce = 0.65% Fe.sup.+.sup.2 /Fe.sup.+.sup.3 = 0.36 Pore        Vol. = 0.0546 cc/g Surface Area = 4.44 m.sup.2 /g                              Cerium added in Aftertreatment                                                 2250 -2    680   772                                                                               880                                                                               920                                                                               978                                                                               1002                                                                              910                                                                               16,000                                                                             --   2.56 15.3 16.75                                                                               91.3                2250 -2    678   775                                                                               880                                                                               920                                                                               975                                                                               1002                                                                              910                                                                               16,150                                                                             --   2.82 15.45                                                                               16.75                                                                               92.2                2250 -2    622   770                                                                               805                                                                               855                                                                               922                                                                               912                                                                               839                                                                               16,250                                                                             --   2.82 16.7 22.65                                                                               73.7                2250 -5    502   658                                                                               750                                                                               798                                                                               865                                                                               792                                                                               773                                                                               16,100                                                                             --   2.82 15.6 30.45                                                                               51.2                                                                           -2250 -5 478 61                                                                8 708 750 783 6                                                                95 711 16,300 1                                                                .86 2.91 11.4 3                                                                8.75 29.4           Table 5                                                                        __________________________________________________________________________     Catalyst (3-6 mm), Ce = 2.85% Pore Vol. = 0.1009 cc/g Surface Area = 13.7      m.sup.2 /g                                                                     Cerium Incorporated before Fusion                                              2000       725   788                                                                               870                                                                               901                                                                               942                                                                               873                                                                               875                                                                               15,700                                                                             2.08 2.87 10.7 17.75                                                                               60.3                2000 -8    730   788                                                                               870                                                                               901                                                                               943                                                                               875                                                                               875                                                                               15,800                                                                             1.75 3.19 10.2 17.75                                                                               57.5                2000 -5    665   745                                                                               805                                                                               828                                                                               842                                                                               780                                                                               800                                                                               15,700                                                                             1.75 3.27 9.8  25.2 38.9                2000 -5    630   700                                                                               738                                                                               742                                                                               740                                                                               701                                                                               724                                                                               15,200                                                                             1.75 3.04 6.51 34.5 18.9                __________________________________________________________________________ 

What is claimed:
 1. In the process of preparing an ammonia synthesis catalyst based on iron oxide, fused and reduced with hydrogen or a mixture of hydrogen and nitrogen, which comprises fusing and reducing the iron oxide, the improvement comprising evacuating air from the pores of the fused and reduced catalyst, impregnating under vacuum the reduced iron oxide with an aqueous solution of a cerium salt, and removing the excess amount of the aqueous solution by drying or draining off.
 2. The process claimed in claim 1, in which the cerium salt comprises cerous nitrate.
 3. The process claimed in claim 1, in which the reduced iron oxide is impregnated with between 0.1 and 1.5% of cerium by weight.
 4. The process claimed in claim 1, in which the reduced iron oxide is impregnated with between 0.3 and 0.8% of cerium by weight.
 5. The process claimed in claim 1, in which the reduced iron oxide is impregnated with between 0.45 and 0.7% of cerium by weight.
 6. An ammonia synthesis catalyst produced in accordance with the method of claim
 1. 7. In the process of preparing an ammonia synthesis catalyst based on iron oxide, fused and reduced with hydrogen or a mixture of hydrogen and nitrogen, and containing traces of a promoter oxide of an element selected from the group consisting of aluminum, calcium, potassium, magnesium and silicon, which comprises fusing and reducing the promoted iron oxide, the improvement comprising evacuating air from the pores of the fused and reduced catalyst, impregnating the reduced promoted iron oxide with an aqueous solution of a cerium salt, and removing the excess amount of the aqueous solution by drying or draining off.
 8. The process claimed in claim 7, in which the cerium salt comprises cerous nitrate.
 9. The process claimed in claim 7, in which the reduced iron oxide is impregnated with between 0.1 and 1.5% of cerium by weight.
 10. The process claimed in claim 7, in which the reduced iron oxide is impregnated with between 0.3 and 0.8% of cerium by weight.
 11. The process claimed in claim 7, in which the reduced iron oxide is impregnated with between 0.45 and 0.7% of cerium by weight.
 12. An ammonia synthesis catalyst produced in accordance with the method of claim
 7. 13. In the process of preparing an ammonia synthesis catalyst based on iron oxide, fused and reduced with hydrogen or a mixture of hydrogen and nitrogen, and containing traces of a promoter oxide of an element selected from the group consisting of aluminum, calcium, potassium, magnesium and silicon, which comprises fusing and reducing the promoted iron oxide, the improvement comprising evacuating air from the pores of the fused and reduced catalyst, impregnating the reduced promoted iron oxide with an aqueous solution of a mischmetal salt, and removing the excess amount of the aqueous solution by drying or draining off.
 14. An ammonia, synthesis catalyst produced in accordance with the method of claim
 13. 